Pyridinium esters



Patented May 2, 1950 UNITED STATES PATENT OFFICE Keiser, Webster Groves, Mo.,

assignors to Petrolite Corporation, Ltd., Wilmington, Del., a

corporation of Delaware No Drawing. Original application June 15, 1942,

Serial No. 447,164. Divided and this application August 2, 1943, Serial No. 497,131

1 Claim. 1

This invention relates to a new chemical product or composition of matter, our present application being a division of our co-pending application Serial No. 447,164, filed June 15, 1942, which subsequently matured as United States Patent No. 2,353,707, dated July 18, 1944.

The main object of our invention is to provide a new chemical product or compound that is particularly adapted for use as a demulsifier in the resolution of crude oil emulsions.

Another object of our invention is to provide a practicable method for manufacturing said new chemical product or compound.

Although one of the primary objects of our invention is to provide a new compound or composition of matter that is an efficient demulsifier for crude oil emulsions of the water-in-oil type, the said compound or composition of matter is adapted for use in other arts, as hereinafter indicated. It also may have additional uses in various other fields which have not yet been investigated.

We have discovered that if one oxyalkylates glycerol so as to introduce at least three oxyalkylene radicals for each hydroxyl group, and if the product so obtained is reacted with a polybasic carboxy acid having not over eight carbon atoms, and in such a manner as to yield a fractional ester, due to the presence of at least one free carboxyl radical, one can then esterify said acidic material or intermediate product with at least one mole of an alcoholic compound of the type herein described to give a variety of new compositions of matter which have utility in various arts, and particularly in the demulsification of crude oil.

The compounds herein contemplated may be produced in any suitable manner, but are usually manufactured by following one of two general procedures. In one of said procedures the oxyalkylated glycerol, which is, in essence, a polyhydric alcohol, is reacted with a polybasic acid so as to give an acidic material or intermediate product, which, in turn, is reacted with an alcoholic body of the kind hereinafter described, and

momentarily indicated by the formula R1(OI-I)m. Generically, the alcoholic body herein conteman intermediate product, and then react said intermediate product or fractional ester with the selected oxyalkylated glycerol.

Glycerol may be conveniently indicated by the following formula:

a polybasic carboxy acid be indicated by the formula:

coon

R-OOOH GOOH then the acyclic reaction product of one mole of oxyethylated glycerol and one mole of a polybasic carboxy acid may be indicated by the following formula:

oiniowoooawoornn I n(C2HAO)n'H zHl n'H in which n" has the value of one or two. Similarly, if two moles of the polybasic acid be used,

then the compound may be indicated by the following formula:

oimmfl ooomc 0011).."

o,H, o1H,0), ooomooomfl" (C:H4O)MH Likewise, if three moles of a polybasic acid are employed, the compound may be indicated by the following formula:

OHH4O)11'OOOR(COOH),,II

OaH -(O:H O),. OOOR(COOH),.-

(oirnomo oomcoom u If a fractional ester of the kind exemplified by the three preceding formulas is reacted with one or more moles of an alcohol of the kind previously described in a generic sense as R1(OH) m, then of the type herein contemplated may be obtained by oxyalkylating agents, without being limited to ethylene oxide. Suitable oxyalkyl'ating agents include ethylene oxide, propylene oxide, butylene oxide and glycid, which, although not included, strictly speaking, by the unitarystructure Gui 1211.0, is included within the meaning of the hereto appendedclaims and maybe simply considered as a variant of propylene oxide, 1. e., hydroxypropylene oxide; Similarly, wherea carboxylic hydrogen atom appears, it may be replaced by metal, an ammonium radical, or substituted ammonium radical, or by an organic group derived from an alcohol, such as an aliphatic alcohol, an 'aralkyl alcohol, or an allcyclic alcohol. It may also be converted into an amide; including a polyaminoamide. Thus, the preceding formulamay be rewritten in its broader scope, asiollows:

.ing-which n replaces, the numbersZ, 3 or i, Z includes the acidic hydrogen atom itself. In the above formula, and hereafter for convenience, R1 is intended to include any hydroxyl groups that remain.

If the compounds herein contemplated are obtained under usual conditions, at the lowest temperatures, thenth'emonomeric for-m is most like- The production of the-compounds h'ereincontemplated is the result of one or moreesterification steps. As. is. well known, esterification procedures can be carried out in various manners, but generally speaking, esterifications can be carried out at the lowest feasible temperatures by using one or several procedures. One procedure is to pass an inert dried gas through, the

mass to;be esterifiedandhave present at the same time a sm'all-am-ount of i a catalyst, such as dried HCl gas, a dried sulfonic acid, or the like. Another and better procedure, in many instances, is to employ the vapors of a suitable liquid, so as to remove any water formed and condense both the vapors of the liq'uid'employed and the water in such amanner. as to trapout the water andr'etur'n the-liquid to the reacting vessel. This suitable conditions, instead of obtaining the moriomeric compounds indicated, one would, in reality, obtain a polymer in the sense, for example, that polyethylene glycols represent a polymer of ethylene glycol. The term polymer is frequently used to indicate the polymerized product derived from a monomer in which the polymer "has the same identical composition as the monomer; In the present instance, however, polymerization involves the splitting and loss of water so that the process; is; essentially self-esterification. 'i hus,'strictly. speaking, the polymeric compounds are not absolutely isomers of the monomeric compounds, but since, for all practical purposes, they canfbe so indicated, and since such practice is common in the a-rts concerned with materials of this type, it'is so adapted here. Thus, reference in the appended claims to polymers is intended to include the self-esterification products of the monomeric, compounds.

lnview of 'whathasbeen said, and view of the recognized hydrophile properties of the. recurring oxyalkylene linkages, particularly the 'oiiyethylen-e linkageit is apparent thatthe ma terials herein contemplated may'vary fromcomlpoundswhich are clearly water-soluble through self 'emulsifying oils, to materials which are balsam-like sub resinous onsemi-resino-us in nature. The compounds may vary from monomers to polymers, in which the unitary structure appears a number of times, "forinstance, 10 or 12' times. It is to be noteclithattrue resins, i. e., truly insoluble materials of a hard'pla'stic nature, aren'ot liereiirincluded; In otherwords, the polymerizedpcompounds"aresoluble to a fairly definite extent; for instancegat' least 5% in some solvents, such'as water, alcohol, benzene, dichloroethyl etlier', acetone, cresylic acid, acetic acid, ethyl acetate, dioXane, or the like. This 'iss'implylanother wayof stating "that the polymerized" pro'ductcont'emplated must beof'the sub-resinous type, which is commonly referred to 'asan A" resin, for" a" B resihj as' distinguished from a C- resin, which is a highly infusibl'e, in-

soluble resin (see Ellis, Chemistry of'Synthe'tic meanness), pages 862, et seq.)

' Reviewingtn iorm'its-presented, itis obvious that onema obtain compounds'within the scope disclosed, which "contain neither; a free hydroxyl nor'a tree carbonyl group, and one may' also' obtain *a coriipoundof the type inwhichthere is present at least one freeca'rboxyl, or? at least,

'On'e fr'ee hydro'x yl, or both. The word polar has'isometimes'beenused in the arts in this par:-

' ticul'ar sense 'toiindi'c'ate"thepresence o'fat least one free hydroxyl group, or at least, one free carboxyltgroumor both. ln'the case of'the free carb'oxyl group, the "carboxylic hydrogen. atom 'may,';of course, bereplacedibyany icnizablehydrogenfiatom equivalent, such; for example, as

materials are subjected tobxyalkyl'ation and then employed in the same manner as oxyalkylated glycerol, is employed in the present instance, are not contemplated in this specific case, although attention is directed to the same.

Reference is also made to other oxyalkylated compounds which may be used as reactants to replace oxyalkylated glycerol, or oxyallrylated ethylene glycol, which latter reactant is described in an application hereinafter referred to. The reactants thus contemplated include the type in which there is an amino or amido nitrogen atom. Particularly, when present in a low molal type of compound prior to oxyalkylation, reference being made to polyhydroxylated materials, including those having two or three hydroxyl groups, as well as thOse having more than three hydroxyl groups. For instance, the oxyalkylated derivatives, particularly the oxyethylated derivatives of ethyldiethanolamine, bis(hydroxyethyl) acetamide, the acetamide of tris(hydroxymethyl) aminomethane, tctrahydroxylated ethylene diamine, etc. Compounds may also be derived from cyclic oliglycerol and the like.

Furthermore, for convenience, attention is directed to a somewhat similar class of materials which are described in our application Serial No. 401,380, filed July 7, 1941, now Patent 2,324,492, July 20, 1943. Said application involves the use of the same type of alcoholic bodies, for reactants, but is limited, among other things, to the compounds which are essentially symmetrical in na ture, for instance, involving the introduction of two alcoholic residues, whereas, in the present instance, one, two, or three, or more, might be introduced.

As indicated previously, the polybasic acids employed are limited to the type having not more than 8 carbon atoms, for example, oxalic, malonic, succinic, glutaric, adipic, maleic, and phthalic. Similarly, one may employ acids such as fumaric, glutaconic, and various others, such as citric, malic, tartaric, and the like. The selection of the particular tribasic or dibasic acid employed, is usually concerned largely with the convenience of manufacture of the finished ester, and also the price of the reactants. Generally speaking, phthalic acid or anhydride tends to produce resinous materials, and greater care must be employed if the ultimate or final product be of a sub-resinous type. type of polybasic acid is such as to contain six carbon atoms or less. Generally speaking, the higher the temperature employed, the easier it is to obtain large yields of esterified product, although polymerization may be stimulated. Oxalic acid may be comparatively cheap, but it decomposes readily at slightly above the boiling point of water. For this reason it is more desirable to use an acid which is more resistant to pyrolysis. Similarly, when a polybasic acid is available in the form of an anhydride, such anhydride is apt to produce the ester with greater case than the acid itself. For this reason, maleic anhydride is particularly adaptable, and also, everything else considered, the cost is comparatively low on a per molar basis, even though somewhat higher on a per pound basis. Succinic acid or the anhydrid-e has many attractive qualities of maleic anhydride, and this is also true of adipic acid. For purposes of brevity, the bulk of the examples, hereinafter illustrated, will refer to the use of maleic anhydride, although it is understood that any other suitable polybasic acid may be employed. Furthermore, reference is made to derivatives obtained byoxyethylation, although, as

Specifically, the preferred previously pointed out, other oxyalkylating agents may be employed.

As far as the range of oxyethylated glycerols employed as reactants is concerned, it is our preference to employ those in which approximately 15 to 24 oxyethylene groups have been introduced into a single glycerol molecule. This means that approximately five to eight oxyethylene radicals have been introduced for each original hydroxyl group.

The oxyalkylation of glycerol is a well known procedure (see Example 11 of German Patent No. 605,973, dated November 22, 1934, to I. G. Farbenindustrie A. G.). The procedure indicated in the following three examples is substantially identical with that outlined in said aforementioned German patent.

OXYETHYLATED GLYCEROL Example 1 184 pounds of glycerol is mixed with by weight, of caustic soda solution having a specific gravity of 1.383. The caustic soda acts as a catalyst. The ethylene oxide is added in relatively small amounts, for instance, about 44. pounds at a time. The temperature employed is from 150-180 C. Generally speaking, the gauge pressure during the operation approximates 200 pounds at the maximum, and when reaction is complete, drops to zero, due to complete absorption of the ethylene oxide. When all the ethylene oxide has been absorbed and the reactants cooled, a second small portion, for instance, 44 more pounds of ethylene oxide, are added and the procedure repeated until the desired ratio of 15 pound moles of ethylene oxide to one pound mole of glycerol is obtained. This represents 660 pounds of ethylene oxide for 92 pounds of glycerol. Such product has the following composition:

(CgH40)5H OXYETHYLATED GLYCEROL Example 2 The ratio of ethylene oxide is increased to 18 pound moles for each pound mole of glycerol. Otherwise, the same procedure is followed as in Example 1, preceding.

OXYETHYLATED GLYCEROL Example 3 The same procedure is followed as in the two previous examples, except that the ratio of ethylene oxide to glycerol is increased to 21 to 1.

OXYE'I'HYLATED GLYCEROL MALEATE Example 1 One pound mole of oxyethylated glycerol (1 to 15 ratio) prepared in the manner previously described is treated with one pound mole of maleic anhydride and heated at approximately- C. for approximately 30 minutes to 2 hours, with constant stirring, so as to yield a monomaleate.

OXYETHYLATED GLYCEROL MALEATE Example 2 The same procedure is followed as in the preceding example, except that two moles of maleic anhydride are employed so as to obtain the dimaleate instead of the monomaleate, The com 7* position of the product ma -be i'hdicatedbytne following formula:

onauono 0103:0110 OH C3Hl5O3-(O2H4O)5 onmono C.CH:OH.C c on OXYETHYLATED GLYCEROL MALEATE Example 3 The same procedure is followed as in the 'two F preceding examples; except that threemoles of maleic anhydride are employed so as to obtain the trimaleate.

OXYETHYLATED GLYCEROL MALEATE Example 4 The same procedure is employed as in the preceding examples, except that oxyethyla'ted glycer- 01 (ratio 1 to 18) is substituted in place of oxyethylated glycerol (ratio 1 to 15) oXYETnYLAT-ED GLYCEROL MALEATE 7 Example The same procedure is employed as in the preceding examples, except that oxye'thylat'ed glycerol (ratio 1 to 21) is employed instead of oxyethylated glycerol (ratio 1 to or (1 to 13).

Previous reference has been made to an alcoholic body which has been defined generically'by the formula R1(OH)m. The sub-generic class of alcoholic compounds employed as reactants in the manufacture of the present compounds, are hydroxylated substituted pyridin'ium halides or other compounds in which there. is present an anion functionally equivalent to the halide anion,

i. e., an anionic functional equivalent to the chloride or bromide ion. When pyridine combines with a hydrohalide, such as HCl, the compound formed may be indicated either as as [Odo] (pyridine hydrochloride) (pyridinium chloride) Compare with ammonium chloride. Note that as in ammonium chloride, the nitrogen atom has 4 covalences, and the fifth valence is electrovalent.

In such instances where the covalent. hydrogen atom has been replaced by an organic radical, for -instance, an alkyl radical, thecompound is then referred to as an N-alkylpyridinium halide, or

more briefly, simply as an alkylpyridinium' halide. (See Organic Chemistry, Hill and Kelley, p. 790; or Organic Chemistry, Caldwell, p. 655.) Such compound may be illustrated, thus:

[G t d contains in. excess of '7 carbon atoms andcontains at least one alcoholic hydrozi'yl radical.

' When such quaternary'compound prepared, for

example, from triricinolein, so that a'triricinolein 'i'adi'cal 'contributes the major'part'ot the carbon atoms are, the group or radical represented'by R, or the group orradical substituted for the hydrogen atom of thepyridinium radical, maiycontain as m'an y as 59 carbon-atoms, of which 57 were contributed by the triricinolein residue. Thisis illustrated by asubsequent example and "formula. Generally'speaking, the range of 10- 30 carbon atoms represents the mostdesirable type of reactant to be employed. The hydroxyl radical may be present. as part-0f a hydroxy hydrocarbon radical, or it may be present as the part of an acyl radical. For instance, it may be present as part of a ricinoleyl radical, or imilar radical, de- "iived'from 'hydroxys'tearic'acid or the like.

In order to illustrate suitable quaternary reactants ofthe type above described, reference is made to-the following examples. It is-to be noted that'this listis'by no means exhaustive.

INTERMEDIATE REACTAN T Example 1 500 g. of a fatty'ac'id ethanolamide, obtained by reaction of split cocoanut oil (containing all the natural acids, beginning with the caprylic up to the stearic acid, and some oleic acid) with monoe'thanolamine, 330 g. hydrochloride of a fraction of pyridine bases (50% distilling up to 140 C., distilling up to 160, completelysoluble in water) and g; of the mixture of the free pyridine bases, are heated at 100 C. until the product is, for the mostpart, soluble in water and stable towards diluted's'odium' carbonate solution. After being separated from the primary compounds not reacted upon, the mixture of pyridinium-, picoliniuinand other homologous pyridinium compounds obtained, may be further worked up to form a 10% waterysolution.

When working at -160, the reaction is more rapid.

Fur'thermor'e, pure pyridine may be used instead of a mixture of pyridine bases.

The reaction may be indicated in the following BEN 45 manner INTERMEDIATE REACTANT Example 2 l-lydroxyethyl ricinoleoamide derived by reaction between ricinoleic acid and monoethanolamine is substituted for the amide employed in 00. Example -2, preceding.

INTERMEDIATE REACTANT Example 3 A drastically-oxidized cast'oroil having approximately the following characteristics:

Acid number 13.2 to 25.0 Saponification number 230.5 to 274.0 Iodine number 43.5 to 55.0 70 Acet'yl number 164.0to 192.0 nydroxyl value 188.0 to 220.0 Percent unsaponifiable matter 1.1 "Percent nitrogen 0.0 PerC'entSCa 0.0 75Pei'ce'nt'ash Trace is converted into the hydroxyethyl amide by reaction with monoethanolamine. Such amide is substituted for the amide employed in Example 1, preceding.

INTERMEDIATE REACTANT Example 4 One pound mole of castor oil is treated with three pound moles of ethylene oxide at a temperature of 100-200 C. at a gauge pressure of 100 pounds and less than 300 pounds, so as to produce an oxyethylated triricinolein. Such oxyethylated triricinolein is converted into the hydroxyethyl amide in the manner described in Example 3, immediately preceding. Such amide is employed instead of the amide described in Example 1, preceding.

INTERMEDIATE REACTANT Example 5 Phenylstearic acid is prepared in any suitable manner. This is converted into phenylstearic hydroxy ethyl amide, and such amide employed in the manner described in Example 1, preceding.

The manufacture of the above compounds is usually conducted with an excess of the pyridinium base halide, such as the hydrochloride or hydrobromide, and usually in the presence of a significant amount of the free pyridinium base itself. In many instances, however, there is no need to use an excess of the pyridinium base halide, and in fact, no need to have present any of the free pyridinium base itself, or at the most, only a trace of the free base.

INTERMEDIATE REACTAN T Example 6 2% parts of chloracetyl chloride were added slowly to 90 parts of castor oil, while stirring. After the first vigorous reaction had subsided, the mixture was placed under a reflux condenser and was stirred and heated on a steam plate for 6 hours. The evolved HCl gas was then swept out with dry air. Then 16 parts of pyridine were added to the mixture, which was thereupon warmed while stirring for a period of four hours. The product was a red, viscous oil which was nearly solid at room temperature. In water it formed a clear, viscous solution of low surface tension. The product was not precipitated from solution by alkali, alkaline earth-, or heavy metal salts. The compound derived may be indicated in the following manner:

INTERMEDIATE REACTANT Example 7 12 parts of chloracetyl chloride were added with stirring to 90 parts of castor oil. The mixture was warmed on the steam plate for 14. hours, purged of HCl with dry air, and then mixed a a at;

with 8 parts of pyridine. This mixture was left on the steam plate over night. The product was a dark red oil, dispersible in water, and soluble in xylene. At least a predominant portion of this material consisted of a quaternary ammonium salt having the formula:

Bis (hydroxyethyl)ricinoleoamide is substituted for castor oil in the preceding example so as to give a suitable monopyridinium derivative.

INTERMEDIATE REACTANT Example 9 Monoricinolein is substituted for castor oil in Intermediate reactant, Example 7, preceding, so as to yield the monopyridinium derivative.

INTERMEDIATE REACTANT Example 10 Diricinolein is substituted for monoricinolein in the preceding example.

INTERMEDIATE REACTANT Example 11 The ricinoleoamide derived from tris(hyd1"oxymethyhaminomethane is substituted for bis(hydroxyethyl)ricinoleoamide in Intermediate reactant, Example 8, preceding. The reaction may be indicated, thus:

0 11 RON INTERMEDIATE REACTAN T Example 12 The neutral ester derived by esterifying one part of diethylene glycol with 2 parts of ricinoleic acid, is substituted for castor oil in Intermediate reactant, Example '7, preceding, so as to yield the monopyridinium derivative.

INTERMEDIATE REACTANT Example 13 Mannitan monooleate is substituted for castor oil in Intermediate reactant, Example 7, so as to obtain the monopyridinium derivative.

INTERMEDIATE REACTAN T Example 14 accuses" 11 tetradecane' may" be employed. The reaction may be indicated, thus:

'BORDEEEIKQEOQOHQCI-+bi INTERMEDIATE REACTANT Eazample 15 Phenol is reacted with acetone (or diethyl ketone or methyl ethyl ketone) as described in U. S. Patent No. 1,225,748, to Wallace A. Beatty, to give the compound diphenylol methane,

Ca \CH4OH (or the corresponding diethyl or methyl ethyl compound). This compound is hydrogenated as described in British Patent No. 274,439, to give the corresponding dicyclohexylol dialk-yfmethane. The product so obtained may be conveniently considered as a cliol'and substituted in place of the diol used as a reactant in Intermediate reactant, Example 14 preceding.

Compare Intermediate reactant, Examples 8- 15, inclusive, with Intermediate reactant, Examples 6 and '7. Note also that a somewhat similar reactant, which may be employed in the manufacture of Intermediates by the same procedure, is obtained by rea'ctingtwo moles of ricinoleic acid with one mole of ethylene diamine, or one mole of ricinoleic acid with one mole of hydroxyethyl ethylene diamine to give an amide.

INTERMEDIATE REACTANT Example 16 The procedure described in Example '7, preceding, is followed, except that sufficient chloracetyl chloride, and likewise, sufiicient pyridine, is employed'so that a dipyridinium compound is obtained. Thus, this is, in essence,a repetition of Intermediate reactant, Example 6, preceding, which is illustrated by formula.

INTERMEDIATE REACTANT- Example 1? 12 parts of ricinoleo-hydroxymethylamide, 8 parts of anhydrous pyridine hydrochloride, and 20 parts of pyridine are stirred together at 70-80 C. until a test sample of thereaction mixture dissolves in water to give clear solutions. The reaction mixture is then distilled at 60-'l0 C. under reduced pressure to remove pyridine. Acetone is then added to the distillation residue, which is a viscous mass; whereby the new quaternary salt is precipitated in the form of White needles. The new quaternary salt, ricinoleo-methyl pyridinium chloride, thus obtained when purified, if necessary, by recrystallization from acetone, gives analyses corresponding to the formula The new quaternary salt is readily soluble in warm water to give clear foaming solutions.

INTERMEDIATE REACTAN T Example 1 8 Compounds of the following type formula are known:

Obviously, acompound of the above type-or fa; suitable variant thereof may have present an alcoh'ol hydroxyl group. For instance, R may-be derived from ricinoleic acid. Such compound may be treated with ethylene oxide so as to convert the amino hydrogen atom into a hydroxyethyl group.

INTERMEDIATE REACTANT Example 19 Compounds of. the following type are known:

CH3(CH2)(:(IJ(|-N Nhal0gcn .O H

The same sort or" procedure enumerated in the preceding example may be used to assure the presence of an alcoholic hydroxyl. group. This means that, instead of being derived from lauric acid or its equivalent, the compound would be obtained from a hydroxylated acid, such as 'IicinO leic, as in the example immediately preceding.

INTERMEDIATE REACTANT Example 20 0 CaHtOE INTERMEDIATE REACTAN T Example .21

An esterified hydroxy tertiaryamine, such as 1. ethyl diethanolamine or triethanolamine, as exemplified by the following formula:

R C 0 O 02H;

OHOzEh-N orroinl in which RC0 is a fatty acid radical, such as the oleic acid radical or ricinoleic acid radical, is substituted for the l'iydroxylated amide in the type of material exemplified by Examples 1-5, preceding. This may be illustrated in the following manner:

'13 INTERMEDIATE REACTANT Example 22 An esterified polyamine of the following formula type:

RCOOCfl'Ii CQHLOH OHCsH; CgH4OH is substituted for the somewhat analogous monoamino reactant of the preceding example.

INTERMEDIATE REACTAN T Example 23 INTERMEDIATE REACTANT Example 24 A high molal amine, for instance, the amine derived by converting oleic acid, stearic acid, ricinoleic acid, lauric acid, and the like, into the corresponding amide, and then reducing to the nitrile and then further reducing to the amine, is treated with an oxyalkylating agent, such as ethylene oxide, to give a product such as hydroxyethyl dodecylamine, or bis(hydroxyethyl)dodecylamine. Such products are then treated with pyridinium hydrochloride or the equivalent in the manner contemplated in Intermediate reactant, Examples 1-5, preceding, so as to yield a hydroxylated compound.

INTERMEDIATE REACTANT Example 25 The ricinoleic acid amide derived by reaction between ricinoleic acid and tris(hydroxymethyl) aminomethane is reacted with pyridine hydrochloride in the manner illustrated by Intermediate reactant, Examples 1-5, preceding. The reaction may be illustrated, thus:

I RN CHaOH OCH:OH

INTERMEDIATE REACTANT Example 26 2-amino-2-methyl-l-propanol is reacted with ricinoleic acid and the amide so obtained reacted with pyridine hydrochloride in the manner examplified by Intermediate reactant, Examples 1-5, preceding. The reaction may be indicated, thus: o H

R N GHs i Similar reactants include the following: 2- amino 1 butanol; 2 amino-2-methyl-1,3-propane diol; 2-amino-2-ethyl-1,3-propane diol; 1- 3-diamino propanol. Such materials may not only be combined with ricinoleic acid; but in such instances where there is more than one available hydroxyl radical after completion of the intermediate, one may use oleic or naphthenic acid or the like to introduce a high molal acyl group. It is to be noted that some of the pyridinium compounds above described as reactants represent new compositions or compounds. Similarly, analogous materials so derived that there is no residual alcoholic hydroxyl, also represent new types of materials.

COMPLETED MONOMERIC DERIVATIVE Example 1 One pound mole of a product of the kind described under the heading Oxyethylated glycerol maleate, Example 1 is reacted with one pound mole of "Intermediate reactant, Example 6, preferably in the absence of any high boiling hydrocarbon or inert solvent. However, if an inert vaporizing solvent is employed, it is generally necessary to use one which has a higher boiling range than xylene, and sometimes removal of such solvent might present a difficulty. In other instances, however, such high boiling inert vaporizing solvent, if employed, might be permitted to remain in the reacted mass and appear as a constituent or ingredient of the final product. In any event, our preference is to conduct the reaction in the absence of any such solvent and permit the reaction to proceed with the elimination of Water. The temperature of reaction is about 180 to 200 C. and time of reaction about 20 hours.

COMPLETED MONOMERIC DERIVATIVE Example 2 The same procedure is followed as in Completed monomeric derivative, Example 1, preceding, except that the dimaleate described under the heading Oxyethylated glycerol maleate, Example 2 is used instead of the monomaleate. The reaction may be shown as follows:

COMPLETED MONOMERIC DERIVATIVE Example 3 The same procedure is followed as in the two preceding examples, except that the trimaleate is substituted for the monomaleate or dimaleate in the two preceding examples.

COMPLETED MONOMERIC DERIVATIVE Example 4 The same procedure is followed as in Examples 2 and 3, immediately preceding, except that for each pound mole of the maleate, or'each pound through the mixture.

accuses mole of the trimaleate, instead of using one pound mole of. Intermediate reactant, Example 6, as. a reactant, one employs two pound moles.

COMPLETED MONOMER'IC DERIVATIJE Example 5 The same'pr'ocedure is followed as in Example 3, preceding, exceptthat for each pound mole of trimaleat'e, instead of adding one pound mole of intermediate reactant, Example 6, one adds three pound moles of Intermediate reactant, Example 6, for reaction.

CONFPLETED MONOMERIC DERIVATIVE Example 6 Reference to the preceding examples will show that in each and every instance oxyethylated glycerol (ratio 1 to 15) has been employed as a raw material or primary reactant. In the present instance, a more hi hly oxyethylated glycerol is employed, to wit, one involving the ratio of 1 to 18 (see Oxyethylated glycerol maleate, Example 4, preceding).

COMPLETED MONOMERIC DERIVATIVE Example 7 The same procedure is followed as in Example 6, immediately preceding, except that the oxyethylated glycerol employed represents one having an even higher degree of oxyethylation. For example, one indicated by the ratio of 1 to 21 (see Oxyethylated glycerol maleate, Example 5, preceding).

COMPLETED MONOMERIC DERIVATIVE Example 8 The same procedure is followed as in Examples 1 to l, preceding, except that "Intermediate reactant, Example '7 is substituted for Intermediate reactant, Example 6 COMPLETED MONOMERIC DERIVATIVE Example 9 The same; procedure is followed as in Examples 1 to 7, preceding, except that the alcoholic body is the compound derived by reaction between pyridine hydrochloride and bis (hydroxyethyl) ricinoleoamide obtained in turn by reacting ricinoleic acid with diethanolamine.

COMPLETED MONOMERIC DERIVATIVE Example 10 The same procedure is followed as in Examples 1 to 'l, preceding, except that instead of employing Intermediate reactant, Example 6, one employs instead the compound obtained b reaction between pyridine hydrochloride and the ricinoleoamide or tris (hydroxymethyl) aminomethane.

The method of producing such fractional esters is well known. The general procedure is to employ a temperature above the boiling point of water and below the pyrolytic point of the reactants. The products are mixed and stirred constantly during the heating and esterification step. If desired, an inert gas, such as dried nitrogen or dried carbon dioxide, may be passed Sometimes it is desirable to add an esterification' catalyst, such as sulfuric acid, benzene sulfonic acid, or the like. This is the same general procedure as employed in the 16 manufacture of ethylene glycol. dihydrogen diphthalate.

Sometimes esterification is conducted most readily in the presence of an inert solvent, that carries away the water of esterification which may be formed, although as is readily appreciated, such water of esterification is absent when such type of reaction involves an acid anhydride, such as maleic anhydride, and a glycol. However, if water is formed, for instance, when citric acid is employed, then a solvent such as xylene may be present and employed to carry off the water formed. The mixture of xylene vapors and water vapors can be condensed so that the water is separated. The xylene is then returned to the reaction vessel for further circulation. This is a conventional and well known procedure and requires no further elaboration.

In the previous monomeric examples there is a definite tendency, in spite of precautions, at least in a number of instances, to obtain polymeric materials and certain cogeneric by-products. This typical, of course, of organic reactions of this kind, and as is well known, organic reactions per so are characterized by the fact that yields are the exception, rather than the rule, and that significant yields are satisfactory, especialiy in those instances where the by-prodnote or cogeners may satisfactorily serve with the same purpose as the principal or intentional product. This is true in the present instance. In many cases when the compound is manufactured for purposes of demulsiflcation, one is better off to obtain a poylmer in the sense previously described, particularly a polymer whose molecular weight is a rather small multiple or the molecular weight of the monomer, for instance, a polymer whose molecular weight is two, three, four, five, or six times the molecular weight-of the monomer. Polymerization is hastened by the presence of an alkali, and thus, in instances where it is necessary to have a maximum yield of the monomer, it may be necessary to take such precautions that the alkali used in promoting ox'yethylation of glycerol; be removed before subsequent reaction. This, of course, can be done in an simple manner by con version to sodium chloride, sodium sulfate, or any suitable procedure.

In the preceding examples of the Completed monomeric derivative, Examples 1 to 10, inclusive, no reference is made to the elimination of such alkaline catalyst, in view of' the eillectiveness of the low multiple polymers as demulsifiers. Previous reference has been made to the fact that the carboxylic hydrogen atom might be variously replaced b substituents, including organic radicals, for instance, the radicals obtained from alcohols, hydroxylated amines, non-hydroxylated amines, polyhydric alcohols, etc. Obviously, the reverse is also true, in that a free hydroxyl group may be esterified with a selected acid, varying from such materials as ricinoleic acid to oleic acid, including alcohol acids, such as hydroxyacetic acid, lactic acid, ricinoleic acid and also polybasic acids of the kind herein contemplated.

With the above facts in mind, it becomes obvious that what has been previously said as to polymerization, with the suggestion that byproducts or cogeneric materials were formed, may be recapitulated with greater definiteness, and one can readily appreciate that the formation of heat-rearranged derivatives or compounds must take place to a greater or lesser degree. Thus, the products herein contemplated may be characterized by being monomers of the type previously described, or esteriflcation polymers, or the heat-rearranged derivatives of the same, and thus including the heat-rearranged derivatives of both the polymers and the esteriiication monomers, separately and jointly. Although the class of materials specifically contemplated in this instance is a comparatively small and narrow class of a broad genus, yet it is obviously impossible to present any adequate formula which would contemplate the present series in their complete ramification, except in a manner employed in the hereto appended claims.

Although the products herein contemplated vary so broadly in their characteristics, 1. e., monomers through sub-resinous polymers, soluble products, water-emulsifiable oils or compounds, hydrotropic materials, balsams, subresinous materials, semi-resinous materials, and the like, yet there is always present the characteristic unitary hydrophile structure related back to the oxyalkylation, particularly the oxyethylation of the glycerol used as the raw material. When our new product is used as a demulsifier in the resolution of oil field emulsions, the demulsifier may be added to the emulsion at the ratio of 1 part in 10,000, 1 part in 20,000, 1 part in 30,000, or for that matter, 1 part in 40,000. In such ratios it well may be that one cannot differentiate between the solubility of a compound completely soluble in water in any ratio, and a semi-resinous product apparently insoluble in water in ratios by which ordinary insoluble materials are characterized. However, at such ratios the importance must reside in interfacial position and the ability to usurp, preempt, or replace the interfacial position previously occupied perhaps by the emulsifying colloid. In any event, reviewed in this light, the obvious common property running through the entire series, notwlth standing variation in molecular size and physical make-up, is absolutely apparent. Such statement is an obvious oversimplification of the rationale underlying demulsification, and does not even consider the resistance of an interracial film to crumbling, displacement, being forced into solution, altered wetability, and the like. As to amidification polymers, for instance, where Z is a polyaminoamide radical, see what is said subsequently.

COMPLETED POLYMERIC DERIVATIVES IN- CLUDING HEAT-REARRANGED COGENERS Example 1 One selects a polyfunctional monomer of one of the types described under the heading "Completed monomeric derivatives, Examples 1 to '7," and heats the same at a temperature of 220- 240" (2., with constant stirring, for a period of 2 to 60 hours, so as to eliminate sufiicient water, in order to insure that the resultant product has a molecular weight approximately twice that of the initial monomer.

COMPLETED POLYMERIC DERIVATIVES IN- CLUDING HEAT-RElARRAN GED COGENERS Example 2 The same procedure is followed as in the preceding example, except that polymerization is continued, using either a somewhat longer reaction time, or it may be, a somewhat higher temperature, or both, so as to obtain a material having a molecular weight of approximately three to four times that of the initial product.

18 COMPLETED POLYMERIC DERIVATIVES m:

CLUDING HEAT-RELARRANGED COGENERS' v Ewample 3 The same procedure is followed as in Examples 1 and 2, preceding, except that one selects the" polyfunctional monomer from one of the mate-. rials described under the headings Completed monomeric derivative, Examples 8 to 10."

COMPLETED POLYMERIC DERIVATIVESi IN- CLUDING HEAT-REARRANGED COGENERS Example 4 The same procedure is followed as in Examples 1 to 3, preceding, except that one polymerizes a mixture instead of a single monomer, for instance, a mixture of materials of the kind described in Completed monomeric derivative, Example 3, and in Completed monomeric derivative, Example 4, are mixed in molecular proportion and subjected to polymerization in the manner indicated in the previous examples.

It is understood, of course, that the polymer 220 C. for polymerization. Thus, one pound mole of an oxyethylated glycerol polymaleate of the kind described is mixed with one pound mole of a product of the kind described under the head: ing Intermediate reactant, Example 7, and reacted for 20 hours at approximately 220 C., until the mass is homogeneous. It is stirred constantly during reaction. Polyfunctionality may reside in dehydration (etherization) of two hydroxyl groups attached to dissimilar molecules.

The fact that the polymerized and heat-rearranged products can be made in a single step, illustrates a phenomenon which sometimes occurs either in such instances where alcoholic bodies of the kind herein illustrated are contemplated as reactants, or where somewhat kindred alcoholic bodies are employed. The reactants may be mixed mechanically to give a homoeneous mixture, or if the reactants do not mix to give a homogeneous mixture, then early in the reaction stage there is formed, to a greater or lesser degree, sufiicient monomeric materials so that a homogeneous system is present. Subsequently, as reaction continues, the system may become heterogeneous and exist in two distinct phases, one being possibly an oily body of moderate viscosity and the other being a heavier material, which is sticky or sub-resinous in nature. In many instances, it will be found that the thinner liquid material is a monomer and the more viscous or resinous material is a polymer, as previously described. Such product can be used for demulsification by adding a solvent which will mutually dissolve the two materials, or else, by separating the two heterogeneous phases and employing each as if it were a separate product of reaction.

Materials of the kind herein contemplated may find uses as wetting, detergent, and leveling agents in the laundry, textile, and dyeing 19 industry; as wetting agents and, detergents in the acid Washing of fruit, in the acid washing of building stone and brick; ,as a wetting agent and spreader in the application of asphalt in road building and the like; as a constituent of soldering fiux preparations; as: a flotation reagent in the flotation separation of various min- 7 erals; for. flocculationand, coagulation of various aqueous suspensions containing negatively charged particles such as sewage, coal washing waste water,v and various trade wastes and the like; as germicides, insecticides, emulsifiers'for cosmetics, spray oils, water-repellent textile finish, etc. These uses are by no means exhaustive,

However, the most important phase of the. presentinvention, as far as industrial application goes, is concerned with the use of the materials previously described as demul'sifiers for waterin-Qil emulsions, and more specifically, emulsions of water or brine in crude petroleum.

We have found that the particular chemical compounds or reagents herein described may also be used for other urposes, for instance, as a break inducer in doctor treatment of the kind intended to sweeten gasoline.

Chemical compounds of the kind herein described are also of value as surface tension depressants in the acidization of calcareous oilbearing' strata bymeans of strong mineral acid, such as hydrochloric acid. Similarly, some members are effective as surface tension depressants or Wetting agents in the flooding f exhausted oil bearing strata;

Compounds ofthe kind herein described may be used as flooding agents for recovering oil from subterranean strata; Compounds of the kind herein described may be used as demulsifiers, or in particular as surface tension depressants in combination with mineral acid or acidizati'on of oil-bearing strata.

cognizance must be taken of the fact that the surf-ace of the reacting vessel may increase or decrease reaction rate and degree of'p'olymerizatiion, fo-r'i'nstance, an iron reaction vessel speedsup reaction and polymerization, compared with a glass-lined vessel.

It is to be noted that in such instances where the. alcoholic, body contains: a reactive. amino hydrogen atom, for instance, in the casewhere an acylated hydroxylated polyamine is employed, for example, the ricinoleyl acid ester of hydroxyethyl ethylenediamine, the oxyethylated glycerol maleate might react to form-an amide of maleic acid. In such instances, of course,such type, to wit, the amido type, is contemplated within the scope of the appendedclaims in the particular instance, butelaboration is eliminated, because, it is. unnecessary and. would only incur greater length of descriptive matter. Thus, stated in another way, in all appropriate instances.v the expression esterification polymers in the appended, claim, includes amidification polymers, as wellas esterification polymers.

Having, thus described our invention,.what we claim anddesire tov secure by Letters Patent is:-

A. member selected from the classconsisting of solvent-soluble hydrophile liquid monomeric;

esters and solvent-soluble hydrophile fusible" polymeric esters; said esters. being obtained by an esterification reaction between (a) a hydroxylated substituted pyridinium hydrohalide in which the pyridinium radical is selected from the group consisting of pyridinium and its lower hydrocarbon substituted homologues, containing; as a substituent for the pyridinium hydrogen atom an aliphatically bound radical; free from heterocyclic radicals, containing at least 8 and not more than 59 carbon atoms and having asan integral part thereof at least one alcoholic hydroxyl redical and (b) an acidic fractional ester obtained by esterification reaction in turn between (a) oxyalkylated glycerol obtained bythe action of an alkylene oxide having not-over 3' carbon atoms on glycerol so as to introduce at least 3 and not more than 10' ether linkages in each hydroXyl-containing radical, and (b) a polycarboxy acid selected from the class consisting of oxalic, malonic, succinic, glutaric, adipic,

No references cited. 

